Group III-V type nitride semiconductor device

ABSTRACT

A group III-V type nitride semiconductor device includes a substrate with a crystal structure of rutile type, CaC 2  type, rock salt type, spinel type, NaFeO 2  (II) type or LiAlO 2  (I) type, and a nitride semiconductor layer epitaxially grown thereon. The substrate is selected so that its lattice constant allows good lattice match with respect to the nitride semiconductor layer, or the substrate is adjusted in composition to have such a lattice constant.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a group III-V type nitride semiconductor device, and particularly to reduction of lattice mismatch between a substrate material and a nitride semiconductor formed thereon.

2. Description of the Related Art

The typical substrate material for group III-V type nitride semiconductor devices conventionally includes Al₂ O₃, SiC and the like. Recently, an attempt has been made to use LiAlO₂ and LiGaO₂ as substrate materials for epitaxial growth of a nitride semiconductor layer, as described in "GROWTH AND OPTICAL PROPERTIES OF GaN GROWN BY MBE ON NOVEL LATTICE-MATCHED OXIDE SUBSTRATES", J. F. H. Nicholls et al., Mat. Res. Soc. Symp. Proc., Vol. 395, 1996, Materials Research Society, pp. 535-539. Furthermore, an attempt has been made to use MgAl₂ O₄ as a substrate material, as described in "InGaN Multi-quantum-well structure laser diodes grown on MgAl₂ O₄ substrates", S. Nakamura et al., Appl. Phys. Lett., 68 (1996) pp. 2105-2107.

When Al₂ O₃ is used as a substrate material, however, the lattice mismatch between e.g. GaN and the substrate reaches as high as at least 10%. When a substrate of SiC is used, GaN and AlN cause lattice mismatches of 3.5% and 1.0% with respect to the substrate, respectively. It is thus difficult to epitaxially grow a satisfactory single-crystal nitride semiconductor layer on a conventional Al₂ O₃ or SiC substrate.

Meanwhile, it is said that the lattice mismatches of LiAlO₂ and LiGaO₂ with respect to GaN are -1.45% and 0.19%, respectively. LiAlO₂ has a crystal structure belonging to hexagonal system, and LiGaO₂ has a crystal structure belonging to rhombohedral system similar to hexagonal system. However, the actual crystals of LiAlO₂ and LiGaO₂ have a locally distorted structure.

FIG. 21 shows a crystal structure of LiAlO₂, and FIG. 22 shows that of NaFeO₂. In the both of FIGS. 21 and 22, a larger white circle represents an oxygen atom and a smaller white circle represents a Li atom. A hatched circle in FIG. 21 represents an Al atom, and a hatched circle in FIG. 22 represents a Ga atom. As shown in FIGS. 21 and 22, the lattice sites of oxygen atoms form a shape distorted from an equilateral triangle.

The lattice constants of LiAlO₂ and LiGaO₂ corresponding to a lattice constant of hexagonal crystal of GaN is the distance between oxygen atoms. Tables 1 and 2 shows respective distances between oxygen atoms for LiAlO₂ and LiGaO₂, respectively. As can be seen from these tables, there are different distances between oxygen atoms in LiAlO₂ and LiGaO₂. Thus, it cannot be said that LiAlO₂ and LiGaO₂ are ideal substrate materials for GaN.

                  TABLE 1                                                          ______________________________________                                                      O-O Bonded with Al                                                                           O-O Bonded with Li                                  ______________________________________                                         Atomic Distance (Å)                                                                     2.918 ± 0.004                                                                             3.301 ± 0.005                                                 2.896 ± 0.005                                                                             3.296 ± 0.003                                                 2.737 ± 0.003                                                                             3.430 ± 0.005                                                 2.874 ± 0.004                                                                             2.737 ± 0.003                                    ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                                      O-O Bonded with Ga                                                                           O-O Bonded with Li                                  ______________________________________                                         Atomic Distance (Å)                                                                     3.012 ± 0.006                                                                             3.189 ± 0.006                                                 3.050 ± 0.003                                                                             3.050 ± 0.004                                                 3.032 ± 0.005                                                                             3.182 ± 0.005                                                 3.004 ± 0.006                                                                             3.251 ± 0.006                                                 2.980 ± 0.004                                                                             3.222 ± 0.004                                                 3.021 ± 0.005                                                                             3.360 ± 0.005                                    Average Distance (Å)                                                                    3.016 ± 0.005                                                                             3.209 ± 0.005                                    ______________________________________                                    

It cannot be said either that MgAl₂ O₄ substrate is an ideal substrate for GaN, since it causes a lattice mismatch of 11% with respect to GaN.

SUMMARY OF THE INVENTION

An object of the present invention is to find a substrate material satisfactorily lattice-matched to a nitride semiconductor and improve the characteristics of a group III-V type nitride semiconductor device with use of such a substrate.

A group III-V type nitride semiconductor device according to one embodiment of the present invention is characterized in that it includes a substrate containing an oxide having rutile structure, and a nitride semiconductor layer epitaxially grown on the substrate, and that the oxide substrate contains one selected from the group consisting of CrO₂, GeO₂ and IrO₂ and one selected from the group consisting of MoO₂, NbO₂, OsO₂, RuO₂, TiO₂ and WO₂.

A group III-V type nitride semiconductor device according to another embodiment of the present invention is characterized in that it includes a substrate containing an oxide having calcium carbide structure, and a nitride semiconductor layer epitaxially grown on the substrate. The oxide with calcium carbide structure preferably contains CaO₂ and one selected from the group consisting of BaO₂ and SrO₂.

A group III-V type nitride semiconductor device according to another embodiment of the present invention is characterized in that it includes a substrate containing an oxide having rock salt structure, and a nitride semiconductor layer epitaxially grown on a crystal plane of the substrate, and that the oxide contains one selected from the group consisting of CoO, MgO, MnO, NbO, NiO, TaO, TiO and VO and one selected from the group consisting of AmO, BaO, CaO, CdO, EuO, NpO, PaO, PuO, SmO, SrO, UO, YbO and ZrO.

A group III-V type nitride semiconductor device according to still another embodiment of the present invention is characterized in that it includes a substrate containing an oxide having spinel structure, and a nitride semiconductor layer epitaxially grown on the substrate, and that the oxide having spinel structure is formed of one selected from the group consisting of Na₂ MO_(x) W_(1-x) O₄ (0≦x≦1) MgIn₂ O₄ and Mn₂ SnO₄. The oxide having spinel structure may contain CdIn₂ O₄ and one selected from the group consisting of CdCr₂ O₄, CdFe₂ O₄, CdGa₂ O₄ and CdMn₂ O₄.

A group III-V type nitride semiconductor device according to still another embodiment of the present invention is characterized in that it includes a substrate containing an oxide having a crystal structure of NaFeO₂ (II) type, and a nitride semiconductor layer epitaxially grown on the substrate, and that the oxide having a crystal structure of NaFeO₂ (II) type is Li_(x) Na_(1-x) GaO₂ (0≦x≦1).

A group III-V type nitride semiconductor device according to still another embodiment of the present invention is characterized in that it includes a substrate containing an oxide having a crystal structure of LiAlO₂ (I) type, and a nitride semiconductor layer epitaxially grown on the substrate, and that the oxide having a crystal structure of LiAlO₂ (I) type is Li_(x) Na_(1-x) AlO₂ (0≦x≦1).

The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross section of a nitride semiconductor laser device formed on a CrNbO₂ substrate.

FIG. 2 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 1.

FIG. 3 is a cross section of a nitride semiconductor laser device formed on a CaBaO₂ substrate.

FIG. 4 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 3.

FIG. 5 is a cross section of a nitride semiconductor laser device formed on a MgYbO substrate.

FIG. 6 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 5.

FIG. 7 is a cross section of a nitride semiconductor laser device formed on a Na₂ MoO₄ substrate.

FIG. 8 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 7.

FIG. 9 is a cross section of a nitride semiconductor laser device formed on a Na₂ WO₄ substrate.

FIG. 10 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 9.

FIG. 11 is a cross section of a nitride semiconductor laser device formed on a CdGaInO₄ substrate.

FIG. 12 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 11.

FIG. 13 is a cross section of a nitride semiconductor laser device formed on a MgIn₂ O₄ substrate.

FIG. 14 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 13.

FIG. 15 is a cross section of a nitride semiconductor laser device formed on a Mn₂ SnO₄ substrate.

FIG. 16 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 15.

FIG. 17 is a cross section of a nitride semiconductor laser device formed on a LiNaGaO₂ substrate.

FIG. 18 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 17.

FIG. 19 is a cross section of a nitride semiconductor laser device formed on a LiNaAlO₂ substrate.

FIG. 20 is a graph representing a relation between the current and optical output in the laser device shown in FIG. 19.

FIG. 21 is a diagram schematically showing a crystal structure of LiAlO₂ type.

FIG. 22 is a diagram showing a crystal structure of NaFeO₂ (II) type.

DESCRIPTION OF THE PREFERRED EMBODIMENTS First Embodiment

The first embodiment employs a substrate formed of an oxide with rutile structure. The substrate can be fabricated by e.g. zone melting method or Czochralski method.

FIG. 1 is a schematic cross section of a blue laser device formed on a (001) surface of a Cr₀.32 Nb₀.68 O₂ substrate. Successively grown in the laser device on a Cr₀.32 Nb₀.68 O₂ substrate 1 are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.2 Ga₀.8 N barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.9 In₀.1 N active layer 4 (layer thickness: 5 nm), a p-type Al₀.2 Ga₀.8 N barrier layer 5 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 2×10¹⁸ cm⁻³) by the MOCVD method. The laser device is also provided with an n-type electrode 7 and a p-type electrode 8.

The blue laser device shown in FIG. 1 is fabricated using the cleavage of the Cr₀.32 Nb₀.68 O₂ substrate and is cleaved to have a cavity length of 1 mm. N-type electrode 7 is formed on n-type GaN contact layer 2 partially exposed by reactive ion beam etching (RIBE). P-type electrode 8 is adapted to have a stripe width of 10 μm.

FIG. 2 is a graph representing a relation between current and optical output when the laser device shown in FIG. 1 is excited at a pulse width of 1 μsec and a pulse period of 1 msec. More specifically, the horizontal axis represents current (A) and the vertical axis represents optical output (in an arbitrary unit) in the graph of FIG. 2. As can be seen from FIG. 2, the threshold current of the laser device of FIG. 1 is approximately 0.5 A, which is approximately half the threshold voltage of conventional laser devices with a MgAl₂ O₄ substrate. This is believed to be attributed to the improvement in crystal quality of group III-V type nitride semiconductor layer included in the laser device shown in FIG. 1.

In using a (001) plane of a Cr_(x) Nb_(1-x) O₂ substrate, the composition ratio between Cr and Nb can be appropriately adjusted to obtain a lattice mismatch of 0% with respect to GaN in principle and hence a nitride semiconductor layer having a better crystal quality than in using conventional substrates. Furthermore, a GaN layer grown on a (001) plane of a Cr_(x) Nb_(1-x) O₂ substrate has zincblende structure which reflects the rutile structure of the substrate. This means that the substrate used is not limited to a Cr_(x) Nb_(1-x) O₂ substrate and may be a substrate of an oxide containing at least one selected from the group consisting of CrO₂, GeO₂ and IrO₂ and at least one selected from the group consisting of MoO₂, NbO₂, OsO₂, RuO₂, TiO₂ and WO₂. Table 3 indicates lattice constants in such oxides and GaN.

                  TABLE 3                                                          ______________________________________                                         Compound      Lattice Constant (Å)                                         ______________________________________                                         CrO.sub.2     4.41                                                             GeO.sub.2     4.395                                                            α-MnO.sub.2                                                                            4.395                                                            IrO.sub.2     4.49                                                             (cubic-GaN)   (4.497)                                                          MoO.sub.2     4.86                                                             NbO.sub.2     4.77                                                             OsO.sub.2     4.51                                                             RuO.sub.2     4.51                                                             TiO.sub.2     4.593                                                            WO.sub.2      4.86                                                             ______________________________________                                    

As can be seen from Table 3, at least one selected from CrO₂, GeO₂ and IrO₂ smaller in lattice constant than GaN and at least one selected from MoO₂, NbO₂, OsO₂, RuO₂, TiO₂ and WO₂ larger in lattice constant than GaN or AlGaN can be appropriately combined to obtain an oxide used as a substrate so that the lattice constant of the substrate is approximately equal to that of GaN.

Second Embodiment

The second embodiment employs a substrate formed of an oxide having calcium carbide structure. The substrate can be fabricated by zone melting method or Czochralski method.

FIG. 3 is a cross section of a blue laser device formed on a (001) plane of a Ca₀.49 Ba₀.51 O₂ substrate. Grown in the laser device on a Ca₀.49 Ba₀.51 O₂ substrate 21 successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.2 Ga₀.8 N barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.9 In₀.1 N active layer 4 (layer thickness: 5 nm), a p-type Al₀.2 Ga₀.8 N barrier layer 5 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 2×10¹⁸ cm⁻³) by the MOCVD method. The laser device is also provided with n- and p-type electrodes 7 and 8.

The laser device shown in FIG. 3 is fabricated by a method similar to that in the first embodiment and is similar in dimensions and shape to the first embodiment.

FIG. 4 represents a relation between current and optical output when the laser device shown in FIG. 3 is excited at a pulse width of 1 μsec and a pulse period of 1 msec. The threshold current of the laser device shown in FIG. 3 is approximately 0.6 A, which is approximately half the threshold current of conventional laser devices. This is believed to be attributed to the improvement in crystal quality of group III-V type nitride semiconductor layer.

In using a (001) plane of a Ca_(x) Ba_(1-x) O₂ substrate, the composition ratio between Ca and Ba can be appropriately adjusted to obtain a lattice mismatch of 0% with respect to GaN and hence a nitride semiconductor layer with a better crystal quality than in using conventional substrates. Furthermore, a GaN layer grown on the (001) plane of Ca_(x) Ba_(1-x) O₂ substrate has zincblende structure which reflects the calcium carbide structure of the substrate. This means that the substrate used is not limited to a Ca_(x) Ba_(1-x) O₂ and may be a substrate of an oxide containing CaO₂ and at least one selected from the group consisting of BaO₂ and SrO₂. Table 4 indicates the lattice constants of these oxides together with that of GaN.

                  TABLE 4                                                          ______________________________________                                         Compound      Lattice Constant (Å)                                         ______________________________________                                         CaO.sub.2     3.54                                                             (cubic-GaN)   (4.497)                                                          BaO.sub.2     5.384                                                            SrO.sub.2     5.03                                                             ______________________________________                                    

As can be seen from Table 4, CaO₂ smaller in lattice constant than GaN and at least one of BaO₂ and SrO₂ larger in lattice constant than GaN can be appropriately combined to render the lattice constant of the substrate approximately equal to that of GaN.

Third Embodiment

The third embodiment employs a substrate formed of an oxide having rock salt structure. Such a substrate can be fabricated by zone melting method or Czochralski method.

FIG. 5 is a cross section of a blue laser device formed on a (111) plane of a Mg₀.57 Yb₀.43 O substrate. Grown in the laser device on a Mg₀.57 Yb₀.43 O substrate successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.1 Ga₀.9 N barrier layer 33 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.95 In₀.05 N/Ga₀.8 In₀.2 N triple quantum well active layer 34 (layer thickness: 5 nm/10 nm), a p-type Al₀.1 Ga₀.9 N barrier layer 35 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 2×10¹⁸ cm⁻³) by the MOCVD method. The laser device also includes n- and p-type electrodes 7 and 8.

The laser device shown in FIG. 5 is fabricated in a method similar to that in the first embodiment and is similar in dimensions and shape to the first embodiment.

FIG. 6 represents a relation between current and optical output when the laser device shown in FIG. 5 is excited at a pulse width of 1 μsec and a pulse period of 1 msec. As shown in FIG. 6, the threshold current of the laser device shown in FIG. 5 is approximately 0.4 A and is thus found to be significantly decreased as compared with conventional laser devices. This is believed to be attributed to the improvement in crystal quality of group III-V type nitride semiconductor layer.

In using a (111) plane of a Mg_(x) Yb_(1-x) O substrate, the composition ratio between Mg and Yb can be appropriately adjusted to obtain a lattice mismatch of 0% with respect to GaN in principle and hence a nitride semiconductor layer having a better crystal quality than in using conventional substrates. Furthermore, a GaN layer grown on the (111) plane of Mg_(x) Yb_(1-x) O substrate has wurtzite structure which reflects rock salt structure of the substrate. This means that the substrate used is not limited to a Mg_(x) Yb_(1-x) O substrate and may be a substrate of an oxide by appropriate combination of at least one selected from the group consisting of CoO, MgO, MnO, NbO, NiO, TaO, TiO and VO and at least one selected from the group consisting of AmO, BaO, CaO, CdO, EuO, NpO, PaO, PuO, SmO, SrO, UO, YbO and ZrO. Table 5 indicates the lattice constants of these oxides together with that of GaN.

                  TABLE 5                                                          ______________________________________                                         Compound   Lattice Constant on (111) plane (Å)                             ______________________________________                                         CoO        3.017                                                               MgO        2.978                                                               MnO        3.143                                                               NbO        2.977                                                               NiO        2.948                                                               TaO        2.984-3.139                                                         TiO        2.953                                                               VO         2.872                                                               (hex-GaN)  (3.18)                                                              AmO        3.571                                                               BaO        3.905                                                               CaO        3.402                                                               CdO        3.320                                                               EuO        3.635                                                               NpO        3.543                                                               PaO        3.508                                                               PuO        3.507                                                               SmO        3.527                                                               SrO        3.649                                                               UO         3.479                                                               YbO        3.437                                                               ZrO        3.267                                                               ______________________________________                                    

As can be seen from Table 5, at least one selected from the group consisting of CoO, MgO, NbO, NiO, TaO, TiO and VO smaller in lattice constant than GaN or AlGaN and at least one selected from the group consisting of AmO, BaO, CaO, CdO, EuO, NpO, PaO, PuO, SmO, SrO, UO, YbO and ZrO larger in lattice constant than GaN or AlGaN can be appropriately combined to obtain an oxide substrate so that the lattice constant of the substrate is approximately equal to that of GaN or AlGaN.

For a substrate with rock salt structure, a nitride semiconductor layer is preferably grown on a (111) plane thereof. The other crystal planes of the substrate is not adapted with respect to the crystal structure of the nitride semiconductor layer and thus is not suitable for obtaining a good single-crystal nitride semiconductor layer.

Fourth Embodiment

The fourth embodiment employs a substrate formed of an oxide with spinel structure. The substrate can be fabricated by zone melting method or Czochralski method.

FIGS. 7 and 9 are cross sections of blue laser devices formed on a (100) plane of a Na₂ MoO₄ substrate 41 and a (111) plane of a Na₂ WO₄ substrate 42. Grown in these laser devices on each of the (100) plane of Na₂ MoO₄ substrate 41 and the (111) plane of Na₂ WO₄ substrate 42 successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type GaN barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.7 In₀.3 N active layer 44 (layer thickness: 5 nm), a p-type GaN barrier layer 45 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 2×10¹⁸ cm⁻³) by the MOCVD method. The laser devices shown in FIGS. 7 and 9 are each provided with n- and p-type electrodes 7 and 8.

The laser devices shown in FIGS. 7 and 9 are each fabricated by a method similar to that employed in the first embodiment and are similar in dimensions and shape to the first embodiment.

FIGS. 8 and 10 respectively represents relations between current and optical output when the laser devices shown in FIGS. 7 and 9 are excited at a pulse width of 1 μsec and a pulse period of 1 msec. The threshold currents of the laser devices shown in FIGS. 7 and 9 are approximately 0.45 A, and 0.4 A, respectively, and thus are significantly reduced as compared with conventional laser devices. This is believed to be attributed to the improvement in crystal quality of group III-V type nitride semiconductor layer.

Table 6 indicates the lattice constants of Na₂ MoO₄ and Na₂ WO₄ as well as that of GaN. In Table 6, a_(cubic) represents respective lattice constants on a (100) plane of substrates and a lattice constant of GaN corresponding thereto, and a_(hex) represents respective lattice constants on a (111) plane of substrates and a lattice constant of GaN corresponding thereto.

                  TABLE 6                                                          ______________________________________                                         Compound          a.sub.cubic                                                                           a.sub.hex                                             ______________________________________                                         Na.sub.2 MoO.sub.4                                                                               4.495  3.178                                                 Na.sub.2 WO.sub.4 4.495  3.178                                                 GaN               4.497  3.18                                                  ______________________________________                                    

As can be seen from Table 6, either the Na₂ MoO₄ substrate or the Na₂ WO₄ substrate has its lattice constant almost matched to that of GaN and use of these substrates allows GaN layers with better crystal qualities than in using conventional substrates. These GaN layers each have a crystal structure which reflects spinel structure of the substrate. The GaN layer grown on a (100) plane of the Na₂ MoO₄ substrate having cubic structure has zincblende structure belonging to cubic system. The GaN layer grown on a (111) plane of the Na₂ WO₄ substrate has a structure similar to side c of hexagonal crystal and thus has wurtzite structure belonging to hexagonal system. The difference in threshold current between the laser devices shown in FIGS. 7 and 9 is attributed to the difference in crystal structure of the nitride semiconductor layers in the devices. It should be noted that Na₂ Mo_(x) W_(1-x) O₄ (0≦x≦1) can also be used as a substrate having spinel structure.

Fifth Embodiment

The fifth embodiment employs a substrate with spinel structure, as in the fourth embodiment.

FIG. 11 is a cross section of a blue laser device formed on a (111) plane of a CdGa₀.54 In₁.46 O₄ substrate. Grown in the laser device on a (111) plane of CdGa₀.54 In₁.46 O₄ substrate 51 successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.2 Ga₀.8 N barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.9 In₀.1 N active layer 4 (layer thickness: 5 nm), a p-type Al₀.2 Ga₀.8 N barrier layer 5 (layer thickness: 0.8 μn, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 2×10¹⁸ cm⁻³) by the MOCVD method. The laser devices also includes n- and p-type electrodes 7 and 8.

The laser devices shown in FIG. 11 is fabricated by a method similar to that employed in the first embodiment and is similar in dimensions and shape to the first embodiment.

FIG. 12 represents a relation between current and optical output when the laser device shown in FIG. 11 is excited at a pulse width of 1 μsec and a pulse period of 1 msec. As shown in FIG. 12, the threshold current of the laser device shown in FIG. 11 is approximately 0.6 A, which is approximately half that of conventional laser devices. This is believed to be attributed to the improvement in crystal quality of nitride semiconductor layer.

In using a CdGa_(x) In_(2-x) O₄ substrate, the composition ratio between Ga and In can be appropriately adjusted to obtain a lattice mismatch of 0% with respect to GaN in principle and hence a nitride semiconductor layer with better crystal quality than in using conventional substrates. A nitride semiconductor layer of InGaN, GaN or AlGaN grown on a (111) plane of the CdGa_(x) In_(2-x) O₄ substrate has wurtzite structure. This means that the substrate used is not limited to a CdGa_(x) In_(2-x) O₄ substrate and can be a substrate formed of an oxide obtained by appropriately combining CdIn₂ O₄ and at least one selected from the group consisting of CdCr₂ O₄, CdFe₂ O₄, CdGa₂ O₄ and CdMn₂ O₄. Table 7 indicates the lattice constants of these oxides as well as that of GaN.

                  TABLE 7                                                          ______________________________________                                         Compound          a.sub.cubic                                                                           a.sub.hex                                             ______________________________________                                         CdCr.sub.2 O.sub.4                                                                               4.284  3.029                                                 CdFe.sub.2 O.sub.4                                                                               4.345  3.072                                                 CdGa.sub.2 O.sub.4                                                                               4.195  2.966                                                 CdMn.sub.2 O.sub.4                                                                               4.110  2.906                                                 (GaN)             4.497  3.18                                                  CdIn.sub.2 O.sub.4                                                                               4.584  3.241                                                 ______________________________________                                    

As can be seen from Table 7, CdIn₂ O₄ larger in lattice constant than GaN and at least one selected from the group consisting of CdCr₂ O₄, CdFe₂ O₄, CdGa₂ O₄ and CdMn₂ O₄ smaller in lattice constant than GaN can be appropriately combined to obtain a substrate so that the lattice constant of the substrate is almost equal to that of GaN.

Sixth Embodiment

The sixth embodiment also employs a substrate with spinel structure.

FIGS. 13 and 15 are cross sections of blue laser devices formed on a (100) plane of a MgIn₂ O₄ substrate and a (111) plane of a Mn₂ SnO₄ substrate, respectively. Grown on each of a (100) plane of a MgIn₂ O₄ substrate 61 and a (111) plane of a Mn₂ SnO₄ substrate 62 successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.2 Ga₀.8 N barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm³), an i-type Ga₀.9 In₀.1 N active layer 4 (layer thickness: 5 nm), a p-type Al₀.2 Ga₀.8 N barrier layer 5 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³) by the MOCVD method. The laser devices each include n- and p-type electrodes 7 and 8.

The laser devices shown in FIGS. 13 and 15 are each fabricated by a method similar to that employed in the first embodiment and is similar in dimensions and shape to the first embodiment.

FIGS. 14 and 16 represent relations between current and optical output when the laser devices shown in FIGS. 13 and 15 are excited at a pulse width of 1 μsec and a pulse period of 1 msec. As shown in FIGS. 14 and 16, the laser devices shown in FIGS. 13 and 15 are approximately 0.7 A and are thus reduced as compared with those of conventional laser devices. This is believed to be attributed to the improvement in crystal quality of nitride semiconductor layer included in the laser devices shown in FIGS. 13 and 15.

                  TABLE 8                                                          ______________________________________                                         Compound          a.sub.cubic                                                                           a.sub.hex                                             ______________________________________                                         MgIn.sub.2 O.sub.4                                                                               4.405  3.114                                                 Mn.sub.2 SnO.sub.4                                                                               4.433  3.134                                                 GaN               4.497  3.18                                                  ______________________________________                                    

Table 8 indicates the lattice constants of MgIn₂ O₄ and Mn₂ SnO₄ as well as that of GaN. Since the lattice mismatches between the GaN layer and substrates are not sufficiently small in the sixth embodiment, as can be seen from Table 8, the reduction in threshold current is smaller than in the other embodiments.

It should be noted that a GaN layer grown on a (100) plane of a MgIn₂ O₄ substrate has zincblende structure and a GaN layer grown on a (111) plane of a Mn₂ SnO₄ substrate has wurtzite structure.

Seventh Embodiment

FIG. 17 is a cross section of a blue laser device formed on a (110) plane of a Li₀.5 Na₀.5 GaO₂ substrate. Grown in the laser device on a (110) plane of a Li₀.5 Na₀.5 GaO₂ substrate 71 successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.2 Ga₀.8 N barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.9 In₀.1 N active layer 4 (layer thickness: 5 nm), a p-type Al₀.2 Ga₀.8 N barrier layer 5 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), by the MBE method. The laser device also includes n- and p-type electrodes 7 and 8.

The laser device shown in FIG. 17 is also fabricated by a method similar to that employed in the first embodiment and is similar in dimensions and shape to the first embodiment.

FIG. 18 represents a relation between current and optical output when the laser device shown in FIG. 17 is excited at a pulse width of 1 μsec and a pulse period of 1 msec. As shown in FIG. 18, the threshold current of the laser device shown in FIG. 17 is approximately 0.6 A and is thus reduced as compared with those of conventional laser devices. This is believed to be attributed to the improvement in crystal quality of nitride semiconductor layer.

When a LiGaO₂ substrate is used, the lattice positions of oxygen atoms form a shape distorted from an equitriangle, as shown in FIG. 22. Since the distance between oxygen atoms bonded with Ga is approximately 3 Å and the distance between oxygen atoms bonded with Li is approximately 3.2 Å, as indicated in Table 2, the substrate is not matched in lattice to GaN. Accordingly, a GaN layer grown directly on such a substrate has a poor crystal quality. In order to lattice-match this substrate to Al₀.2 Ga₀.8 N used as a clad layer, the distance between oxygen atoms bonded with Ga need be increased and the inventors have thus discovered use of the substrate according to the present embodiment in which Na is added to LiGaO₂ to increase the distance between oxygen atoms bonded with Ga.

Eighth Embodiment

FIG. 19 is a cross section of a blue laser device formed on a (001) plane of a Li₀.3 Na₀.7 AlO₂ substrate. Grown in the laser device on a (001) plane of a Li₀.3 Na₀.7 AlO₂ substrate 81 successively are an n-type GaN contact layer 2 (layer thickness: 0.1 μm, carrier concentration: 5×10¹⁸ cm⁻³), an n-type Al₀.2 Ga₀.8 N barrier layer 3 (layer thickness: 1.0 μm, carrier concentration: 5×10¹⁷ cm⁻³), an i-type Ga₀.9 In₀.1 N active layer 4 (layer thickness: 5 nm), a p-type Al₀.2 Ga₀.8 N barrier layer 5 (layer thickness: 0.8 μm, carrier concentration: 5×10¹⁷ cm⁻³) and a p-type GaN contact layer 6 (layer thickness: 0.1 μm, carrier concentration: 2×10¹⁸ cm⁻³) by the MBE method. The laser device also includes n- and p-type electrodes 7 and 8.

The laser device shown in FIG. 19 is also fabricated by a method similar to that employed in the first embodiment and is similar in dimensions and shape to the first embodiment.

FIG. 20 represents a relation between current and optical output when the laser device shown in FIG. 19 is excited at a pulse width of 1 μsec and a pulse period of 1 msec. As shown in FIG. 20, the threshold current of the laser device shown in FIG. 19 is approximately 0.6 A and is thus reduced as compared with those of conventional laser devices. This is believed to be attributed to the improvement in crystal quality of nitride semiconductor layer.

When a LiAlO₂ substrate is used, the lattice sites of oxygen form a shape distorted from an equitriangle, as shown in FIG. 21. Since the interatomic distance between oxygen bonded with Al is approximately 2.9 Å and the distance between oxygen atoms bonded with Li is approximately 3.2 Å, as indicated in Table 1, the substrate is not matched in lattice to GaN. Accordingly, a nitride semiconductor layer grown on such a substrate has a poor crystal quality. Particularly, in order to lattice-match the substrate to Al₀.2 Ga₀.8 N used as a clad layer, the distance between oxygen atoms bonded with Al in the substrate need be increased and the inventors have thus discovered that a substrate in which the distance between oxygen atoms bonded with Al is increased by adding Na to LiAlO₂ can be used for epitaxial growth of nitride semiconductor layer.

Although the eighth embodiment describes that a nitride semiconductor layer of GaN type is grown on a substrate, a semiconductor layer of AlGaN type or InGaN type may be grown on the substrate.

By thus employing the substrates discovered by the Inventors, the lattice mismatch can be reduced with respect to a III-V type nitride semiconductor layer epitaxially grown thereon and the characteristics of a group III-V type nitride semiconductor device can be significantly improved.

Although the present invention has been described and illustrated in detail, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims. 

What is claimed is:
 1. A group III-V type nitride semiconductor device characterized in that it comprises:a substrate containing an oxide having calcium carbide structure; and a nitride semiconductor layer epitaxially grown on said substrate.
 2. The group III-V type nitride semiconductor device according to claim 1, characterized in that said oxide contains CaO₂ and at least one oxide selected from the group consisting of BaO₂ and SrO₂.
 3. A group III-V type nitride semiconductor device comprising:a substrate containing an oxide having rock salt structure; and a nitride semiconductor layer epitaxially grown on a (111) plane of said substrate; the device characterized in thatsaid oxide contains at least one oxide selected from the group consisting of CoO, MgO, NbO, NiO, TaO, TiO, and VO and at least one oxide selected from the group consisting of AmO, BaO, CaO, CdO, EuO, NpO, PaO, PuO, SmO, SrO, UO, YbO and ZrO.
 4. A group III-V type nitride semiconductor device comprising:a substrate containing an oxide having spinel structure; and a nitride semiconductor layer epitaxially grown on said substrate; the device characterized in thatsaid oxide is Na₂ Mo_(x) W_(1-x) O₄ (0≦x≦1).
 5. A group III-V type nitride semiconductor device comprising:a substrate containing an oxide having calcium carbide structure; and a nitride semiconductor layer epitaxially grown on said substrate; the device characterized in thatsaid oxide is Ca_(x) Ba_(1-x) O₂ (0≦x≦1).
 6. A group III-V type nitride semiconductor device comprising:a substrate containing an oxide having calcium carbide structure; and a nitride semiconductor layer epitaxially grown on said substrate; the device characterized in thatsaid oxide is Mg_(x) Yb_(1-x) O (0≦x<1).
 7. A group III-V type nitride semiconductor device comprising:a substrate containing an oxide having wurtzite structure; and a nitride semiconductor layer epitaxially grown on said substrate; the device characterized in thatsaid oxide is Mn₂ SnO₄. 